Summary: Suspension polymerization yielded microspheres (40–50 μm) of polyacrolein. Smooth and rugged surfaces can be created by varying the polymerization procedure. We have shown that the polyacrolein resins with a high loading of aldehyde groups serve as effective scavengers for primary amines and may be used to remove compounds bearing amino groups in the combinatorial synthesis of compound libraries. Copolymerization with styrene can help to separate the adjacent aldehyde groups, thus making the functional groups more available in organic reactions. The polyacrolein resins in the aldehyde form or after appropriate chemical modifications may also be useful as support materials in solid‐phase synthesis.